Positive photosensitive resin composition, process for its preparation, and semiconductor devices

ABSTRACT

A positive photosensitive resin composition having high sensitivity is provided which can form patterns with high resolution and high film thickness retention and can give by curing film excellent in mechanical characteristics, adhesion, and water absorption. This composition comprises 100 parts by weight of an alkali-soluble resin, 1 to 100 parts by weight of a photosensitive diazoquinone compound (B) and a filler (C), the content (F) of the filler(C) as defined by the following formula ranging from 2 to 70 wt %. F=filler (C)/(alkali-soluble resin+filler (C))

TECHNICAL FIELD

[0001] The present invention relates to a positive photosensitive resincomposition of high sensitivity which can form a pattern of highresolution and high residual film ratio, which contains a filler andthereby is superior in mechanical properties, adhesivity and waterabsorptivity, and which can be developed with an aqueous alkalisolution; as well as to a process for producing such a resincomposition. The present invention relates further to a semiconductordevice produced by using the present positive photosensitive resincomposition.

BACKGROUND ART

[0002] Polymide resins superior in heat resistance and outstanding inelectrical properties, mechanical properties, etc. have been used in thesurface-protecting film and interlayer dielectric of a semiconductorchip. Meanwhile, in recent years, semiconductor chips have become morehighly integrated and larger, resin-encapsulated packages have becomethinner and smaller, and surface mounting by reflow soldering has cometo be adopted; for these and other reasons, significant improvements inheat cycle resistance, thermal shock resistance, etc. have come to berequired for polyimide resins, and a polymide resin of higherperformance has become necessary.

[0003] Meanwhile, attention has recently been paid to a technique ofallowing a polyimide resin itself to have photosensitivity.Photosensitive polyimide resins include, for example, one represented bythe following formula (3).

[0004] Use of the above resin enables simplification of a part ofpattern formation step and shortening of the step but requires, indevelopment, a solvent such as N-methyl-2-pyrrolidone or the like,posing a problem in safety and handling. Hence, positive photosensitiveresins which can be developed with an aqueous alkali solution, have beendeveloped recently. In, for example, JP-B-1-46862 there is disclosed apositive photosensitive resin constituted by a polybenzoxazole precursorand a diazoquinone compound. This resin has high heat resistance,excellent electrical properties and fine processability, and is usableas a wafer-coating resin and further may be used as a resin forinterlayer insulation. As to the mechanism of development of thispositive photosensitive resin, the diazoquinone compound which isinsoluble in aqueous alkali solution when unexposed to a light, givesrise to a chemical change when exposed to a light and becomes soluble inaqueous alkali solution. Owing to this difference in solubility inaqueous alkali solution between exposed portion and unexposed portion,it is possible to form a coating pattern constituted by the unexposedportion alone.

[0005] In recent years, photosensitive resins have been stronglyrequired to have, in particular, a high sensitivity. The reason is that,with a low sensitivity, the exposure time per one wafer is long,resulting in a low through-put. In order for a photosensitive resin tohave a high sensitivity, it is considered to, for example, make smallerthe molecular weight of a polybenzoxazole as a base resin. With thisapproach alone, however, film thinning of unexposed portion duringdevelopment is large, making it impossible to obtain a desired filmthickness and, moreover, giving a pattern of inferior shape. Further,the cured film formed by thermal dehydration and ring closure issignificantly low in mechanical properties. For these reasons, it hasbeen desired to develop a photosensitive resin satisfying the aboveproperties and yet having a high sensitivity.

[0006] In addition, in recent years, wafers, in particular, have becomelarger and wafers of 300 mm have come to be used. With a large wafer,however, warpage arises owing to a difference in linear expansioncoefficient between silicon wafer and photosensitive resin and there areproblems, for example, cracking of wafer in back side grinding step forwafer thinning. Therefore, it has been desired to develop aphotosensitive resin of low stress having a linear expansion coefficientclose to that of silicon wafer.

DISCLOSURE OF THE INVENTION

[0007] The present invention aims at providing a positive photosensitiveresin of high sensitivity which can be developed with an aqueous alkalisolution, which can form a pattern of high resolution and high residualfilm ratio, and which can give a cured film superior in mechanicalproperties, adhesivity and water absorptivity.

[0008] The present invention lies in a positive photosensitive resincomposition comprising 100 parts by weight of an alkali-soluble resin, 1to 100 parts by weight of a photosensitive diazoquinone compound (B) anda filler (C), characterized in that content F of the filler (C)represented by the following formula is 2 to 70% by weight.

F=filler (C)/[alkali-soluble resin+filler (C)]

[0009] In a preferred embodiment of the present positive photosensitiveresin composition, the alkali-soluble resin is a polyamide (A)represented by the following general formula (1); a phenol compound (D)represented by the following general formula (2) is contained in anamount of 1 to 30 parts by weight relative to 100 parts by weight of thealkali-soluble resin; the filler (C) is selected from the groupconsisting of silica, aluminum oxide and zirconium oxide; and the filler(C) has particle diameters of 1 nm to 1,000 nm:

[0010] wherein X is a tetravalent aromatic group; Y is a bivalentaromatic group; Z is a group represented by

[0011] wherein R₁ and R₂ are each a bivalent organic group, and R₃ andR₄ are each a monovalent organic group; a and b are each a molefraction; a+b=100 mole %; a=60.0 to 100.0 mole %; b=0 to 40.0 mole %;and n=2 to 500,

[0012] wherein R₅ and R₆ are each hydrogen atom or an alkyl group; andR₇, R₈, R₉ and R₁₀ are each one atom or group selected from hydrogenatom, halogen atom, hydroxyl group, alkoxy group, cycloalkyl group andalkyl group.

[0013] The present invention lies also in a process for producing apositive photosensitive resin composition, which comprises dispersing afiller (C) in a solution by use of a dispersing agent and thendissolving, in the resulting solution, an alkali-soluble resin and aphotosensitive diazoquinone compound (B).

[0014] The present invention lies also in a semiconductor deviceproduced by using the above positive photosensitive resin composition,preferably a semiconductor device for mounting of a flip chip.

BRIEF DESCRIPTION OF THE DRAWING

[0015]FIG. 1 is a schematic sectional view showing an example of thesemiconductor device of the present invention.

[0016] In FIG. 1, individual numerals refer to the followings.

[0017] 1: silicon wafer; 2: Al pad; 3: passivation film; 4: buffercoating film; 5: metal (e.g. Cr or Ti) film; 6: wiring (e.g. Al or Cu);7: insulating film; 8: barrier metal; 9: solder bump

DETAILED DESCRIPTION OF THE INVENTION

[0018] As the alkali-soluble resin, there are, for example,hydroxypolyamide, polyamic acid and phenolic novolac. In order tosatisfy both heat resistance and photosensitivity, hydroxypolyamide ispreferred, and one represented by the general formula (1) isparticularly preferred.

[0019] The polyamide (A) represented by the general formula (1) ismainly constituted by a bisaminophenol having an X structure and adicarboxylic acid having a Y structure. The polyamide (A), when heatedto about 300 to 400° C., gives rise to ring closure and changes to apolybenzoxazole which is a heat-resistant resin.

[0020] The X of the polyamide (A) of the present invention representedby the general formula (1) includes, for example,

[0021] wherein A is —CH₂—, —C(CH₃)₂—, —O—, —S—, —SO₂—, —CO—, NHCO— or—C(CF₃)₂—; however, is not restricted thereto.

[0022] Of these, one giving a composition of particularly highsensitivity is selected from the followings.

[0023] The Y of the general formula (1) includes, for example,

[0024] wherein A is —CH₂—, —C(CH₃)₂—, —O—, —S—, —SO₂—, —CO—, —NHCO— or—C(CF₃)₂—; however, is not restricted thereto.

[0025] Of these, one giving a composition of particularly highsensitivity is selected from the followings.

[0026] The Z of the general formula (1) includes, for example,

[0027] ; however, is not restricted thereto.

[0028] The Z of the general formula (1) is used, for example, when, inparticular, adhesivity is needed against a substrate such as siliconwafer or the like. The proportion b of Z used is maximum 40 mole %. Whenb is more than 40 mole %, the resin is very low in solubility and scumis formed, making patterning impossible. X, Y and Z may be each used inone or more kinds.

[0029] The photosensitive diazoquinone compound (B) used in the presentinvention is a compound having a 1,2-benzoquinone diazide or1,2-naphthoquinone diazide structure and is a known substance in U.S.Pat. Nos. 2,772,972, 2,797,213 and 3,669,658. There can be mentioned,for example, the followings.

[0030] In the above, each Q is hydrogen atom or

[0031] Of these, particularly preferred are the followings from thestandpoint of high residual film ratio.

[0032] In the above, each Q is selected from hydrogen atom or

[0033] and, in each compound, at least one Q is

[0034] The amount of the photosensitive diazoquinone compound (B) addedto the alkali-soluble resin is 1 to 100 parts by weight relative to 100parts by weight of the alkali-soluble resin. When the addition amount isless than 1 part by weight, patterning ability of the resin is inferior.Meanwhile, when the addition amount is more than 100 parts by weight,the degree of tensile elongation of the film formed is extremely low.

[0035] In order to enhance the photosensitivity of the positivephotosensitive resin composition of the present invention, it ispossible to add, as necessary, a dihydroxypyridine derivative to thecomposition. As the dihydroxypyridine derivative, there can bementioned, for example,2,6-dimethyl-3,5-diacetyl-4-(2′-nitrophenyl)-1,4-dihydroxypyridine,4-(2′-nitrophenyl)-2,6-dimethyl-3,5-dicarboethoxy-1,4-dihydroxypyridine,and4-(2′,4′-dinitrophenyl)-2,6-dimethyl-3,5-carbomethoxy-1,4-dihydroxypyridine.

[0036] The filler (C) used in the present invention includes an organicfiller, an inorganic filler and a pigment. These may be used singly orin admixture of two or more kinds. The organic filler includes, forexample, epoxy resin, melamine resin, urea resin, acrylic resin,phenolic resin, polyimide resin, polyamide resin, polyester resin andteflon resin. As the inorganic filler, there are used metal oxide fineparticles of alumina, silica, magnesia, ferrite, aluminum oxide,zirconium oxide or the like, or fine particles of silicate (e.g. talc,mica, kaolin or zeolite), barium sulfate, calcium carbonate, fullereneor the like. The above fillers are used singly or in admixture of two ormore kinds. Aluminum oxide and zirconium oxide are particularlypreferred because they produce no thixotropy after mixing and enableuniform coating by a spinner. Silica is also preferred from thestandpoints of linear expansion coefficient of cured material and cost.

[0037] The filler (C) is preferred to be fine particles having anaverage particle diameter of 1 to 1,000 nm and more preferred to be fineparticles having an average particle diameter of 1 to 100 nm. An averageparticle diameter of more than 1,000 nm is not preferred because itincurs a reduction in resolution and sensitivity. An average particlediameter of less than 1 nm makes mixing difficult.

[0038] The content F of the filler (C) is represented by the followingformula.

F=filler (C)/[alkali-soluble resin+filler (C)]

[0039] The content F (based on weight) of the filler is 2 to 70% byweight, preferably 2 to 50% by weight. A content of less than 2% byweight shows no addition effect. A content of more than 70% by weightresults in an extremely long development time or no formation of curedfilm.

[0040] The pigment used in the present invention includes, for example,a coloring pigment such as titanium oxide or the like.

[0041] In the positive photosensitive resin composition of the presentinvention, it is preferred that a phenol compound (D) represented by thegeneral formula (2) is also contained.

[0042] wherein R₅ and R₆ are each hydrogen atom or an alkyl group; andR₇, R₈, R₉ and R₁₀ are each one atom or group selected from hydrogenatom, halogen atom, hydroxyl group, alkoxy group, cycloalkyl group andalkyl group.

[0043] The technique of adding the phenol compound to a positive resistcomposition is disclosed in, for example, JP-A-3-200251, JP-A-3-200252,JP-A-3-200253, JP-A-3-200254, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260,JP-A-4-12356 and JP-A-4-12357. However, the phenol compounds mentionedin these literatures show a small sensitivity increase when used in thepositive photosensitive resin composition of the present invention usinga polyamide as the base resin.

[0044] Meanwhile, when the phenol compound of the present inventionrepresented by the general formula (2) is used, the dissolution rate ofexposed portion is high, resulting in an increased sensitivity. Further,film thinning of unexposed portion which is seen when the molecularweight of the alkali-soluble resin is made smaller for increasedsensitivity, is very small.

[0045] In the present invention, it was found out that addition of thephenol compound represented by the general formula (2) provides afurther advantage that a positive photosensitive resin compositionimproved in adhesion against an encapsulating resin can be obtained.

[0046] As the compound represented by the general formula (2), there canbe mentioned the followings, but the compound is not restricted thereto.

[0047] Of these, particularly preferred compounds from the standpoint ofsensitivity and residual film ratio are as follows.

[0048] The phenol compound (D) represented by the general formula (2)may be used solely but may also be used in combination with a phenolcompound mentioned in the above literatures. In the latter case, thephenol compound represented by the general formula (2) occupies 50% byweight or more of the total phenol compounds.

[0049] The amount of the total phenol compounds used is preferably 1 to50 parts by weight relative to 100 parts by weight of the alkali-solubleresin. The amount of the phenol compound (D) represented by the generalformula (2) is preferably 1 to 30 parts by weight relative to 100 partsby weight of the alkali-soluble resin. When the amount is less than 1part by weight, there is no sensitivity increase. When the amount ismore than 30 parts by weight, there is a large reduction in residualfilm ratio, precipitation takes place during cryopreservation, and thereis no practical applicability.

[0050] To the positive photosensitive resin composition of the presentinvention there can be added, as necessary, additives such as levelingagent, silane coupling agent and the like.

[0051] In the present invention, these components are dissolved in asolvent and are used in a varnish form. As the solvent, there can beused, for example, N-methyl-2-pyrrolidone, γ-butyrolactone,N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether,propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, methyl lactate, ethyllactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butyleneglycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate andmethyl-3-methoxypropionate, singly or in admixture.

[0052] With regard to a process for producing the positivephotosensitive resin composition of the present invention, it ispreferred that in mixing the filler, the alkali-soluble resin, thephotosensitive material, etc. into an organic solvent or the like, thefiller is uniformly dispersed in the resulting resin composition. Hence,in order to prevent secondary agglomeration of the filler, the filler isbeforehand dispersed uniformly in the solvent using a dispersing agentand then the alkali-soluble resin, the photosensitive material, etc. aredissolved to obtain a uniform varnish. As the dispersing agent, therecan be mentioned, for example, an anionic active agent, a cationicactive agent, a nonionic active agent and an amphoteric active agent. Ofthese, a cationic active agent and a nonionic active agent arepreferred. Of these, a phosphoric acid ester type active agent ispreferred.

[0053] Dispersion can be conducted by a known method. For example, byusing a dispersing machine of high shear force such as ball mill, rollmill, diamond mill or the like, there can be obtained a photosensitiveresin composition of good dispersion and mixing. For better dispersionand mixing, it is possible to add a wetting agent, a dispersing agent, asilane coupling agent, a titanium coupling agent, an antifoaming agent,etc., or to make the filler hydrophobic beforehand.

[0054] In using the positive photosensitive resin composition of thepresent invention, first, the composition is coated on an appropriatesubstrate, for example, a silicon wafer, a ceramic or an aluminumsubstrate. The coating is conducted by spin coating using a spinner,spray coating using a spray coater, dipping, printing, roll coating,etc. Next, prebaking is conducted at 60 to 120° C. to dry the coatingfilm and then an actinic ray is applied in a desired pattern shape. Asthe actinic ray, there can be used an X ray, an electron beam, anultraviolet light, a visible light, etc. with one having a wavelength of200 to 500 nm being preferred. Next, the exposed portion is dissolvedand removed using a developing solution to obtain a relief pattern.

[0055] As the developing solution, there can be suitably used an aqueoussolution of alkali such as inorganic alkali (e.g. sodium hydroxide,potassium hydroxide, sodium carbonate, sodium silicate, sodiummetasilicate or ammonia water), primary amine (e.g. ethylamine orn-propylamine), secondary amine (e.g. diethylamine or di-n-propylamine),tertiary amine (e.g. triethylamine or methyldiethylamine), alcoholamine(e.g. dimethylethanolamine or triethanolamine), quaternary ammonium salt(e.g. tetramethylammonium hydroxide or tetraethylammonium hydroxide) orthe like; or an aqueous solution obtained by adding, to the aboveaqueous alkali solution, an appropriate amount of a water-solubleorganic solvent (e.g. methanol or ethanol) or a surfactant. Developmentcan be conducted by using spray, paddle, dipping, ultrasonic wave or thelike. Then, the relief pattern formed by development is rinsed.Distilled water is used as a rinsing liquid. Then, a heat treatment isapplied to form an oxazole ring and obtain a final pattern of high heatresistance.

[0056] The positive photosensitive resin composition of the presentinvention can be used to produce a semiconductor device of highreliability. When the resin composition is used to produce, inparticular, a semiconductor device for mounting of a flip chip, asignificant reduction in cost is obtained also. The positivephotosensitive resin composition of the present invention is useful notonly in semiconductor device but also in interlayer insulation ofmulti-layered circuit, cover coating of flexible copper-clad board,solder resist film and the like. Their production can be conducted by aconventional method except that the positive photosensitive resincomposition of the present invention is used.

[0057] An example of the semiconductor device produced using thepositive photosensitive resin composition of the present invention isdescribed referring to FIG. 1.

[0058]FIG. 1 is an enlarged sectional view of the pad portion of asemiconductor device having a bump, of the present invention.

[0059] As shown in FIG. 1, on a silicon wafer 1, a passivation film 3 isformed on an Al pad 2 for input and output. In the passivation film 3 isformed a via hole. Thereon is formed a polybenzoxazole resin film (abuffer coating film 4). The film 4 is exposed to a light using a g-linestepper, then dipped in a developing solution to dissolve and remove theexposed portion, and rinsed with pure water for 30 seconds to obtain apattern. Then, curing is conducted in a clean oven in a nitrogenatmosphere at 150° C. for 30 minutes, at 250° C. for 30 minutes and at350° C. for 30 minutes in this order. Then, reactive ion etching (RIE)is conducted to etch the passivation film 3. Thereon is formed a metal(e.g. Cr or Ti) film 5 by sputtering so that the film 5 is connected tothe Al pad 2. The metal film 5 is etched and removed at the periphery ofa solder bump 9 for insulation between individual pads.

[0060] Next, a wiring 6 is formed by plating. Then, a positivephotosensitive resin is coated and a pattern (an insulating film 7) isformed via a photolithography step. Then, a barrier metal 8 and solderare formed by plating. Then, a flux is coated, followed by heating todissolve the solder. Then, the flux is washed to form a solder bump 9 toobtain a structure of FIG. 1. This structure is diced along a scribingline to obtain individual chips.

BEST MODE FOR CARRYING OUT THE INVENTION

[0061] The present invention is specifically described below by way ofExamples.

EXAMPLE 1

[0062] Synthesis of Polyamide

[0063] 1 mole of diphenyl ether-4,4′-dicarboxylic acid was reacted with2 moles of 1-hydroxybenzotriazole. 492.5 parts by weight (1 mole) of theresulting dicarboxylic acid derivative and 347.9 parts by weight (0.95mole) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane were fedinto a four-necked separable flask provided with a thermometer, astirrer, a raw material inlet and a dry nitrogen gas-introducing tube.3,000 parts by weight of N-methyl-2-pyrrolidone was added fordissolution. Then, a reaction was conducted at 75° C. for 12 hours on anoil bath.

[0064] Then, the reaction mixture was collected by filtration and pouredinto a water/methanol (3/1) solution. The resulting precipitate wascollected by filtration, washed with water thoroughly, and dried undervacuum to obtain an intended polyamide (A-1).

[0065] Production of Positive Photosensitive Resin Composition

[0066] 10 parts by weight of silica (C-1, average particle diameter: 100nm, specific surface area: 40 m²/g) and 1 part by weight of a surfactant(Phosphanol RE-610, a product of Toho Chemical Industry Co., Ltd.) weredispersed in 250 parts by weight of γ-butyrolactone using a diamondmill. Therein were added and dissolved 100 parts by weight of thepolyamide (A-1) synthesized above and 25 parts by weight of adiazoquinone (B-1) having a structure shown later. Then, filtration wasconducted using a 1-μm Teflon filter to obtain a photosensitive resincomposition.

[0067] Evaluation of Properties

[0068] This positive photosensitive resin composition was coated on asilicon wafer using a spin coater, followed by drying on a hot plate at120° C. for 4 minutes, to obtain a coating film having a thickness ofabout 7 μm. The coating film was exposed to a light via a reticle, usinga g-line stepper NSR-1505G3A (a product of Nikon Corporation), at from50 mJ/cm² to 540 mJ/cm² with an increment of each 20 mJ/cm².

[0069] Then, the light-exposed coating film was dipped in a 2.38%aqueous tetramethylammonium hydroxide solution for 40 seconds todissolve and remove the exposed portion, followed by rinsing with purewater for 30 seconds. As a result, there was pattern formation from thearea at which an exposure of 290 mJ/cm² was made, and there was no scumat the pattern bottom (sensitivity was 290 mJ/cm2). At this time, theresidual film ratio (film thickness after development/film thicknessbefore development) was very high at 92.0%.

[0070] Separately, the positive photosensitive resin composition wascoated on two silicon wafers in the same manner; then, prebaking wasconducted; and heating was made in an oven at 150° C. for 30 minutes, at250° C. for 30 minutes and at 350° C. for 30 minutes in this order tocure the resin. The cure shrinkage was 15%.

[0071] Then, the coated silicon wafer was dipped in a 2% aqueoushydrogen fluoride solution to peel the cured film from the siliconwafer. The peeled film was washed thoroughly with water, dried andmeasured for linear expansion coefficient by thermal mechanical analysis(TMA). A low value of 3.7×10⁻⁵ 1/° C. was obtained. Separately, thecured film was dipped in pure water for 24 hours and measured for waterabsorption. It was 0.2%.

EXAMPLE 2

[0072] In the polyamide synthesis of Example 1, there were used 348parts by weight (0.95 mole) of2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 12.4 parts byweight (0.05 mole) of1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, whereby wassynthesized a polyamide of the general formula (1) wherein X is X-1shown later, Y is Y-1 shown later, Z is Z-1, a=95, and b=5. The sameevaluation as in Example 1 was made.

EXAMPLE 3

[0073] In Example 1, the diazoquinone compound was changed to B-2 shownlater. The same evaluation as in Example 1 was made.

Example 4

[0074] In Example 1, 10 parts by weight of a phenol compound (P-1) wasadded to the positive photosensitive resin composition. The sameevaluation as in Example 1 was made.

EXAMPLE 5

[0075] In Example 4, the amount of the phenol compound (P-1) added waschanged to 5 parts by weight. The same evaluation as in Example 4 wasmade.

EXAMPLE 6

[0076] In Example 1, the silica (C-1) was changed to zirconium oxide(C-2, average particle diameter: 10 nm, specific surface area: 50 m²/g).The same evaluation as in Example 1 was made.

EXAMPLE 7

[0077] In Example 1, the amount of silica was changed to 30 parts byweight. The same evaluation as in Example 1 was made.

COMPARATIVE EXAMPLE 1

[0078] In Example 1, no silica was added. The same evaluation as inExample 1 was made.

COMPARATIVE EXAMPLE 2

[0079] In Example 1, the amount of silica added was increased to 400parts by weight. The same evaluation as in Example 1 was made.

COMPARATIVE EXAMPLE 3

[0080] In Example 1, the amount of silica added was changed to 0.5 partby weight. The same evaluation as in Example 1 was made.

COMPARATIVE EXAMPLE 4

[0081] In Example 1, no Phosphanol RE-610 was added to produce apositive photosensitive resin composition.

[0082] Secondary agglomeration of silica filler took place andfiltration through 1-μm teflon filter was impossible; therefore, it wasunable to obtain a good product. No evaluation was made.

COMPARATIVE EXAMPLE 5

[0083] 100 parts by weight of the above-synthesized polyamide (A-1) wasdissolved in 250 parts by weight of γ-butyrolactone. Therein wasdissolved 25 parts by weight of a diazoquinone (B-1) having a structureshown later. Then, solid silica was added, followed by stirring. Therewas no uniform dispersion of silica; filtration through 1-μm teflonfilter was impossible; therefore, it was unable to obtain a goodproduct. No evaluation was made.

[0084] The resin components used in Examples 1 to 7 and ComparativeExamples 1 to 5 are shown below.

[0085] wherein each Q is hydrogen atom or

[0086] and 70% of the total Q's is

[0087] wherein each Q is hydrogen atom or

[0088] and 70% of the total Q's is

[0089] The formulations of the resin compositions used in Examples 1 to7 and Comparative Examples 1 to 3 are shown in Table 1. TABLE 1Photosensitive Polyamide material Filler Phenol compound AdditionAddition Addition Addition amount amount amount amount Silicon (weightStruc- (weight Struc- (weight Struc- (weight Amine Acid diamine parts)ture parts) ture parts) ture parts) Example 1 X-1 Y-1 — 100 B-1 25 C-110 — — 2 X-1 Y-1 Z-1 100 B-1 25 C-1 10 — — 3 X-1 Y-1 — 100 B-1 25 C-1 10— — 4 X-1 Y-1 — 100 B-1 25 C-1 10 P-1 10 5 X-1 Y-1 — 100 B-1 25 C-1 10P-1  5 6 X-1 Y-1 — 100 B-1 25 C-1 10 — — 7 X-1 Y-1 — 100 B-1 25 C-1 30 —— Compara- 1 X-1 Y-1 — 100 B-1 25 — — — — tive 2 X-1 Y-1 — 100 B-1 25C-1 400 — — Example 3 X-1 Y-1 — 100 B-1 25 C-1 0.5 — —

[0090] The evaluation results of Examples 1 to 7 and Examples 1 to 3 areshown in Table 2. TABLE 2 Residual Cure Linear Water Sensi- film shrink-expansion absorp- tivity ratio age coefficient tion mJ/cm² % % l/° C. %Example 1 290 92 15 3.7 × 10⁻⁵ 0.2 2 300 90 15 4.0 × 10⁻⁵ 0.2 3 250 9314 3.7 × 10⁻⁵ 0.2 4 230 92 16 3.9 × 10⁻⁵ 0.3 5 240 91 16 3.9 × 10⁻⁵ 0.36 280 93 17 3.7 × 10⁻⁵ 0.2 7 310 90 12 2.5 × 10⁻⁵ 0.3 Compara- 1 350 8620 5.5 × 10⁻⁵ 0.4 tive 2 400 94 3 Film for- ← Example mation wasimpossible. 3 450 87 20 5.5 × 10⁻⁵ 0.4

[0091] As is clear from the above Examples, the present invention hasmade it possible to provide a positive photosensitive resin compositionof high sensitivity which can form a pattern of high resolution and highresidual film ratio and which can give a cured film superior inmechanical properties, adhesivity and water absorptivity. Further, byusing the positive photosensitive resin composition of the presentinvention, a semiconductor device of high reliability can be obtained.

INDUSTRIAL APPLICABILITY

[0092] The positive photosensitive resin composition of the presentinvention can be developed by an aqueous alkali solution, can form apattern of high resolution and high residual film ratio, and can form afilm superior in mechanical properties, adhesivity and waterabsorptivity; therefore, it can be suitably used in a semiconductordevice as a surface-protecting film of a chip or as an interlayerdielectric. A semiconductor device produced using the positivephotosensitive resin composition of the present invention has highreliability and accordingly can be suitably used in computer, TV, andother electric or electronic appliances.

1. A positive photosensitive resin composition comprising 100 parts byweight of an alkali-soluble resin, 1 to 100 parts by weight of aphotosensitive diazoquinone compound (B) and a filler (C), characterizedin that content F of the filler (C) represented by the following formulais 2 to 70% by weight. F=filler (C)/[alkali-soluble resin+filler (C)] 2.A positive photosensitive resin composition according to claim 1,wherein the alkali-soluble resin is a polyamide (A) represented by thefollowing general formula (1):

wherein X is a tetravalent aromatic group; Y is a bivalent aromaticgroup; Z is a group represented by

wherein R₁ and R₂ are each a bivalent organic group, and R₃ and R₄ areeach a monovalent organic group; a and b are each a mole fraction;a+b=100 mole %; a=60.0 to 100.0 mole %; b=0 to 40.0 mole %; and n=2 to500.
 3. A positive photosensitive resin composition according to claim 1or 2, which contains a phenol compound (D) represented by the followinggeneral formula (2) in an amount of 1 to 30 parts by weight relative to100 parts by weight of the alkali-soluble resin:

, wherein R₅ and R₆ are each hydrogen atom or an alkyl group; and R₇,R₈, R₉ and R₁₀ are each one atom or group selected from hydrogen atom,halogen atom, hydroxyl group, alkoxy group, cycloalkyl group and alkylgroup.
 4. A positive photosensitive resin composition according to claim2 or 3, wherein the X in the polyamide (A) of the general formula (1) isselected from the followings.


5. A positive photosensitive resin composition according to claim 2, 3or 4, wherein the Y in the polyamide (A) of the general formula (1) isselected from the followings.


6. A positive photosensitive resin composition according to claim 1, 2,3, 4 or 5, wherein the filler (C) is selected from the group consistingof silica, aluminum oxide and zirconium oxide.
 7. A positivephotosensitive resin composition according to claim 1, 2, 3, 4 or 5,wherein the filler (C) has an average particle diameter of 1 nm to 1,000nm.
 8. A process for producing a positive photosensitive resincomposition, characterized by dispersing a filler (C) in a solution byuse of a dispersing agent and then dissolving, in the resultingsolution, an alkali-soluble resin and a photosensitive diazoquinonecompound (B).
 9. A process for producing a positive photosensitive resincomposition according to claim 8, wherein the alkali-soluble resin is apolyamide (A) represented by the general formula (1).
 10. A process forproducing a positive photosensitive resin composition according to claim8 or 9, wherein the positive photosensitive resin composition contains aphenol compound (D) represented by the general formula (2) in an amountof 1 to 30 parts by weight relative to 100 parts by weight of thealkali-soluble resin and the phenol compound (D) is added after thefiller (C) has been dispersed in the solution by use of the dispersingagent.
 11. A process for producing a positive photosensitive resincomposition according to claim 8, 9 or 10, wherein the filler (C) isselected form the group consisting of silica, aluminum oxide andzirconium oxide.
 12. A process for producing a positive photosensitiveresin composition according to claim 8, 9 or 10, wherein the filler (C)has an average particle diameter of 1 nm to 1,000 nm.
 13. Asemiconductor device produced by using a positive photosensitive resincomposition set forth in any of claims 1 to
 7. 14. A semiconductordevice according to claim 13, which is for mounting of a flip chip.